Oleo resins and phosphate esters for use in pyrotechnic formulations

ABSTRACT

A pyrotechnic formulation, wherein that formulation includes a tricyclic phosphate ester.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Non-Provisional Patent Application claims priority to a U.S. Provisional Patent Application having Ser. No. 62/024,875, filed Jul. 15, 2014, which is hereby incorporated by reference herein.

FIELD OF THE INVENTION

Compositions of matter are disclosed where that composition comprises an oleo resin and/or a phosphate ester.

SUMMARY OF THE INVENTION

Applicant has prepared Aminoborate esters by reacting trialkanolamines and trialkyl borates.

Applicant has prepared pyrotechnic formulations, each of which includes a different tricyclic borate ester.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better understood from a reading of the following detailed description taken in conjunction with the drawings in which like reference designators are used to designate like elements, and in which:

FIG. 1 is a ¹H N MR of Nonivamide Reactant;

FIG. 2A is a ¹NMR of Nonivamide Reactant;

FIG. 2B is a ¹³C NMR of Nonivamide Reactant;

FIG. 3A is a ¹H NMR of Nonivamide-Maleic Anhydride Adduct;

FIG. 3B is a ¹³C NMR of Nonivamide-Maleic Anhydride Adduct;

FIG. 4A is a ¹H NMR of Nonivamide-Phthalic Anhydride Adduct; and

FIG. 4B is a ¹³C NMR of Nonivamide-Phthalic Anhydride Adduct;

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This invention is described in preferred embodiments in the following description with reference to the Figures, in which like numbers represent the same or similar elements. Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.

The described features, structures, or characteristics of the invention may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are recited to provide a thorough understanding of embodiments of the invention. One skilled in the relevant art will recognize, however, that the invention may be practiced without one or more of the specific details, or with other methods, components, materials, and so forth. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of the invention.

The following examples are presented to further illustrate to persons skilled in the art how to make and use Applicant's borate ester compositions. These examples are not intended as a limitation, how

Nonivamide and related oleoresin capsaicin (OC) compounds are known non-lethal agents employed for protective as well as riot and crowd control purposes. Such agents are typically dissolved within solvents (e.g. alcohols, glycols, acetone etc.) and contacted upon assailants via spraying or projectile means. They are typically not dispersed and vaporized via pyrotechnic propellants given their inherent limited thermal stability and susceptibility towards decomposition when heated at high temperatures associated with pyrotechnic propellant combustion (e.g. sugar-chlorate, nitrate or perchlorate pyrotechnic systems found within grenades, smoke pots etc.). In comparison to the former, pyrotechnic devices offer a better means of delivering OC agent in a controlled and more prolonged fashion. Hence there is considerable advantages towards producing versions of OC which are more thermally stable and hence more compatible with conventional pyrotechnic propellants. One means of stabilizing OC entails converting the phenolic hydroxyl on the molecule to a borate, phosphate or carboxylate ester. Such esterification methods are well known to those skilled in the art and include direct esterification between the OC phenolic hydroxyl and boric, phosphoric or carboxylic acid accompanied by water condensation by-product removal, reaction of phenolic with corresponding acid halide, acid anhydride or transesterification with borate, phosphate or carboxylic derived ester having favorable leaving groups. Such reactions may be conducted neat or within a solvent. Examples of ester protected OC reactions are provided below.

EXAMPLE 1 OC Maleate Ester Synthesis

About 0.6230 g of N-vanillylnonivamide (Nonivamide, synthetic capsaicin) (TCI America) was reacted neat at 8° C. with a slight molar excess (0.2097 g) of Maleic Anhydride (Huntsman Chemical) for 15 minutes followed by cooling to room temperature producing a transparent yellow colored viscous oil product. The reaction progress was monitored using ¹H and ¹³C Nuclear Magnetic Resonance (NMR) Spectroscopy whereby downfield shifts in the phenolic aromatic ring hydroxyl group proton and associated carbon atom peaks was observed after maleic anhydride addition to the melt. (See spectra and Table 4 below for NMR Spectral Shifts obtained within deuterochloroform solution using an Anasazi Instruments 90 MHz NMR Spectrometer.)

EXAMPLE 2 OC Phthalate Ester Synthesis

A similar procedure was employed as Example 1 except 0.3580 g of N-vanillylnonivamide (TCI America) was reacted neat at 90° C. with a slight molar excess (0.185 g) of Phthalic Anhydride (Stepan Chemical Company) for 10 minutes which ultimately yielded an off white solid product upon cooling to ambient temperature. The reaction progress was monitored using ¹H and ¹³C Nuclear Magnetic Resonance (NMR) Spectroscopy whereby downfield shifts in the phenolic aromatic ring hydroxyl group proton and associated carbon atom peaks was observed after phthalic anhydride addition to the melt. (See spectra and Table 4 below for NMR Spectral Shifts obtained within deuterochloroform solution using an Anasazi Instruments 90 MHz NMR Spectrometer.)

EXAMPLE 3 OC Succinate Ester Synthesis

The same neat melt reaction approach was employed as the former except 0.3118 g of N-vanillylnonivamide (TCI America) was reacted with 0.1099 g of Succinic Anhydride (TCI America) at 110° C. for 15 minutes. A white colored solid product resulted upon cooling the melt to room temperature and NMR Spectral analysis verified phenolic hydroxyl reaction with this acid anhydride.

TABLE 4 ¹H Peak Chemical ¹³C Peak Chemical Compound Shift (ppm) Shift (ppm) Nonivamide Reactant 6.14 145.36 Nonivamide - Maleic 6.36 147.05, 145.30 Anhydride Adduct Nonivamide - Phthalic 6.30 146.91, 145.20 Anhydride Adduct

Applicant has further found that certain [2.2.2] tricyclic phosphate esters, i.e.

organophosphate cage compounds impart low combustion temperatures to phosphate-containing obscurant formulations. Applicant reacts polyol 1 with phosphorus oxychloride 2 with to form organophosphate tricyclic compound 3.

EXAMPLE 4 R1=CH₂—OH

In certain embodiments, polyol 1 comprises pentaerythritol, wherein Applicant forms tricyclic compound 6.

EXAMPLE 5 R1=CH₂—O—CH₂—(C₄H₆PO₄)

In certain embodiments, polyol 1 comprises dipentaerythritol, wherein Applicant forms tricyclic phosphate ester 8.

EXAMPLE 6 R1=CH₃

In certain embodiments, polyol 1 comprises trimethylolethane 9, wherein Applicant forms tricyclic phosphate ester 10.

EXAMPLE 7

R1=H

In certain embodiments, polyol 1 comprises trimethylolmethane 11, wherein Applicant forms tricyclic phosphate ester 12.

EXAMPLE 8 R1=NH₂

In certain embodiments, polyol 1 comprises Tris(hydroxymethyl) Aminomethane 13, wherein Applicant forms tricyclic phosphate ester 14.

EXAMPLE 9 R1=NO₂

In certain embodiments, polyol 1 comprises Tris(hydroxymethyl) Nitromethane 15, wherein Applicant forms tricyclic phosphate ester 16.

EXAMPLE 10

In this Example 10, Applicant has reacted tricyclic phosphate ester comprising a pendent hydroxyl group 6 with phosphorus oxychloride 2 to give phosphate ester 17.

EXAMPLE 11

In this Example 11, Applicant has reacted tricyclic phosphate ester comprising a pendent hydroxyl group 6 with phosphorus oxychloride 2 to give phosphate ester 18.

EXAMPLE 12

In this Example 12, Applicant has reacted tricyclic phosphate ester 18 with melamine 19 to give phosphate ester 20.

EXAMPLE 13

Applicant has prepared Aminoborate esters by reacting trialkanolamines and trialkyl borates. Borate ester 21 reacts amino-triol 22 to give a tricyclic aminoborate ester 23.

EXAMPLE 14A

Table 5 recites one embodiment of Applicant's pyrotechnic formulation.

TABLE 5 Concentration Component Function (Wgt. %) Melamine Obscurant 20.81 Acetoguanamine Obscurant 30.81 Potassium Chlorate Oxidizer 34.08 Sucrose Fuel 13.55 Nitrocellulose Binder 0.75

EXAMPLE 14B

Applicant reacted triethanolamine with boric acid to give tricyclic aminoborate ester 24. Table 6 recites a pyrotechnic formulation comprising tricyclic aminoborate ester 24. In certain embodiments, Applicant's pyrotechnic formulation comprises about 16.61 weight percent Triethanolamine Borate 24.

TABLE 6 Concentration Component Function (Wgt. %) Potassium Chlorate Oxidizer 33.46 Sucrose Fuel 13.2 Melamine Obscurant Component 21.68 Triethanolamine Borate Obscurant Component 16.61 Acetoguanamine Obscurant Component 14.21 Nitrocellulose Pellet Binder 0.83

EXAMPLE 14C

Applicant reacted triisopropanolamine with boric acid to give tricyclic aminoborate ester 25. Table 7 recites a pyrotechnic formulation comprising tricyclic aminoborate ester 25.

TABLE 7 Concentration Component Function (Wgt. %) Potassium Chlorate Oxidizer 33.46 Sucrose Fuel 13.2 Melamine Obscurant Component 21.68 Triisopropanolamine Borate Obscurant Component 16.61 Acetoguanamine Obscurant Component 14.21 Nitrocellulose Pellet Binder 0.83

In certain embodiments, Applicant's pyrotechnic formulation comprises about 17 weight percent Triethanolamine Borate 25.

EXAMPLE 15

Applicant has replaced the triethanolamine Borate component from EXAMPLE 14/TABLE 5 with each of the tricyclic phosphate esters disclosed hereinabove. TABLE 8 summarizes Applicant's tricyclic phosphate ester pyrotechnic compositions.

In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 6. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 8. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 10. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 12. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 14. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 16. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 17. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 18. In one embodiment, Applicant replaces 16.61 grams of triethanolamine borate with 16.61 grams of tricyclic phosphate ester 20.

TABLE 8 Concentration Component Function (Wgt. %) Potassium Chlorate Oxidizer 33.46 Sucrose Fuel 13.2 Melamine Obscurant Component 21.68 Tricyclic Phosphate Ester Obscurant Component 16.61 Acetoguanamine Obscurant Component 14.21 Nitrocellulose Pellet Binder 0.83

In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 6. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 8. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 10. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 12. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 14. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 16. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 17. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 18. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic phosphate ester 20.

In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic borate ester 24. In one embodiment, Applicant's pyrotechnic formulation comprises about 17 weight percent of tricyclic borate ester 25.

While the preferred embodiments of the present invention have been illustrated in detail, it should be apparent that modifications and adaptations to those embodiments may occur to one skilled in the art without departing from the scope of the present invention. 

I claim:
 1. A pyrotechnic formulation, comprising about 16.61 weight percent triethanolamine Borate.
 2. The pyrotechnic formulation of claim 1, further comprising: acetoguanamine; and nitrocellulose.
 3. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


4. The pyrotechnic formulation of claim 3, further comprising: acetoguanamine; and nitrocellulose.
 5. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


6. The pyrotechnic formulation of claim 5, further comprising: acetoguanamine; and nitrocellulose.
 7. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


8. The pyrotechnic formulation of claim 7, further comprising: acetoguanamine; and nitrocellulose.
 9. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


10. The pyrotechnic formulation of claim 9, further comprising: acetoguanamine; and nitrocellulose.
 11. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


12. The pyrotechnic formulation of claim 11, further comprising: acetoguanamine; and nitrocellulose.
 13. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


14. The pyrotechnic formulation of claim 13, further comprising: acetoguanamine; and nitrocellulose.
 15. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


16. The pyrotechnic formulation of claim 15, further comprising: acetoguanamine; and nitrocellulose.
 17. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


18. The pyrotechnic formulation of claim 17, further comprising: acetoguanamine; and nitrocellulose.
 19. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


20. The pyrotechnic formulation of claim 19, further comprising: acetoguanamine; and nitrocellulose.
 21. A pyrotechnic formulation, comprising a tricyclic phosphate ester having the structure:


22. The pyrotechnic formulation of claim 21, further comprising: acetoguanamine; and nitrocellulose.
 23. A pyrotechnic formulation, comprising a tricyclic borate ester having the structure:

wherein R1 is selected from the group consisting of —CH₂— and —CH(CH₃)—.
 24. The pyrotechnic formulation of claim 23, further comprising: acetoguanamine; and nitrocellulose. 